Substantially anhydrous oil base finish composition for fibrous hydrophobic cellulosic derivatives



United States Patent SUBSTANTIALLY ANHYDROUS OIL BASE FINISH- COMPOSITION FOR FIBROUS HYDROPHOBIC CELLULOSIC DERIVATIVES Harry H; Hall, Drexel Hill, Pa.,. assignor to American ViscoseCorporation, Philadelphia, Pa., a corporation of Delaware No Drawing. Filed Feb. 12, 1958, Ser; No. 714,703

20 Claims. (Cl. 252--8.8)

This invention relates to'the treatment of textile materials and more particularly to the lubrication, softening, and conditioning-of fibrous materials formed. from hydrophobic cellulose derivatives.

Various yarn finish compositions comprising vegetaother substances are chiefly employed as anti-static agents to avoid the generation of excessive static electricity which would make it exceedingly diflicult, if not impossible, to process the fibers. It is: also the accepted practice to incorportate a surface-active emulsifying material in'these compositions so thatitcan'be readily removed prior to dyeing fabrics which have been knitted or woven from the treated fibers. Another commonly employed constituent in such compositions is a softening.

agent which imparts limpness to the relatively stifi hydrophobic fibers and thus assures convenient manipulation of the fibers especially in knitting.

It is evident that there are numerous problems in formulating the above described finish compositions to achieve the desired eifect on the yarn as well as stability of the finish itself. One problem stems from the necessity of using a substantially anhydrous oil-base finish with the hydrophobic cellulose derivatives of this invention and the resulting problem encountered in incorporating an oil-insoluble, water-soluble or water-dispersible anti-static agent therein. Compounds suchas sorbitan esters, polyglycol esters and ethers,*and alkyl-aryl' polyglycols have been proposed as mutual solvents or coupling agents for the two incompatible materials, mineral oil and the anti-static agent, but none of these proposals were completely satisfactory without causing deficiencies in other respects, such as handling, sizing or emulsification.

It has now been discovered that N-hydr'ocarbon-trimethylenediamine dioleate, wherein the hydrocarbon group is a straight chain saturated or unsaturated hydrocarbon radical having from 14 to 18 carbon atoms or a mixture thereof, is a highly effective coupling agent for a water-soluble or water-dispersible anti-static agent and mineral oil in a yarn finish.

The yarn finish contemplated by this invention con-.

tains from 3 to 10 parts by weight of anti-static agent,

from 5 to 17 parts by weight of the dioleate coupling agent and from 50 to 90 parts. by Weightv of mineral oil. It. is preferred to add from 5 to 25 parts by weight of an emulsifier to the finish so that it canbe readily removed from the yarn by washing or scrubbing with an aqueous medium. The emulsifier is necessary for this purpose because the dioleate is substantially insoluble and non-dispersible in water.

Patented Oct. 18, 1960 ice The structure ofthe dioleate coupling agent can be illustrated as follows:

where R is a straight chainliydrocarbon radical having,

8 to 18 carbon atoms such asoctyl, decyl, dodecyl, tetra.- decyl, hexadecyl, octadecyl, or octadecenyl. or mixtures of the same.

The diamines useful for the present'invention are prepared commercially in thefollowing manner:

Heat Catalyst Catalyst where R is an aliphatic hydrocarbon radical containing; 7 to 17 carbonatoms and mixtures of the same. There are several commercial sources of the acid or acids R -d-OH described above. From the standpoint of'availability and cost, the fatty acids derived from naturally occurring fats and oils provide a convenient source, e.g. those derived from tallow wherein comprises a mixture of acids havinga hydrocarbon chain length of 13 to 17 carbon atoms; in other words R is a mixture of aliphatic hydrocarbon radicals having 13 to 17 carbon atoms, or those derived from coconut oil wherein R is a mixture of aliphatic hydrocarbon radicals having8 to 18 carbon atoms. On the other hand, the individual acids, which may be used aswell, are also commercially available; in this instance R is a single aliphatic hydrocarbon containing 8 to 17 carbon atoms.

It is contemplated by the present invention that the dioleate described above effects the dispersion in mineral oil of water-soluble or water-dispersible compounds which are not oil-soluble or oil-dispersible and impart anti-static properties to fibrous materials which would otherwise tend to pick up excessive electrostatic charges when processed. Such compounds are well known in the yarn finish art as anti-static agents. A preferred group of anti-static agents are organic quinquevalent nitrogen compounds such as quaternary ammonium alkylsulfates having attached directly to the nitrogen atoms from 1 to 3 straight chain hydrocarbon radicals which have from 12 to 18 carbons and attached to the-remaining bonds of the nitrogen, alkyl radicals having from 1' to 5 carbon atoms and/or a monocyclic organic radical having five or six members in the ring structure of which the nitrogen atom may be a member. The alkyl-gro'up to which the sulfate group is attached has from 1' to 4 carbon atoms and the alkylsulfat'e group forms the nega: tive ion of' these compounds. Examples of these-preferredl anti-static agents are as follows: oleyl ethyl niorpholinium ethosulfate, cetyl ethyl morpholinium ethosulfate, oleyl methyl morpholinium methosulfate, cetyl methyl morpholinium methosulfate, lauryl methyl morpholinium methosulfate, lauryl ethyl morpholiniumethosulfate, oleyl diethyl imidazolinium .ethosulfate, cetyl diethyl imidazolinium ethosulfate, lauryl diethyl imidazolinium ethosulfate, ethyl oleyl hydroxyethyl imidazolinium ethosulfate, ethyl cetyl hydroxyethyl imidazolinium ethosulfate, ethyl lauryl hydroxyethyl imidazolinium ethosulfate, lauryl triethyllammonium ethosulfate, palmityl triethyl ammonium ethosulfate, oleyl t'riethyl ammonium ethosulfate, dilauryl diethyl ,ammonium ethosulfate, dicetyl diethyl ammonium ethosulfate, dioleyl diethyl ammonium ethosulfate,'dihydroxyethyl lauryl ethyl ammoniumv ethosulfate, dihydroxyethyl cetyl ethyl ammonium ethosulfate, dihydroxyethyl oleyl ethyl ammonium ethosulfate, dilauryl hydroxyethyl ethyl, ammonium ethosulfate, dicetyl hydroxyethyl ethyl ammonium ethosulfate and dioleyl hydroxyethyl ethyl ammonium ethosulfate.

Halogen containing anti-static agents, having a chloride, bromide or iodide ion in place of the sulfate ion in any of the abovedescribed compounds, can be used also. In a like manner, corresponding phosphate compounds can be used. Examples of other anti-static agents which can be dispersed in'mineral oil with the dioleate are lauryl alcohol phosphate, the lauric amide of N-methyl gluca'mine, mannitol (or sorbitol), dilauryl phosphate, dicetyl phosphate, diethanolamine salt of lauryl phosphate, triethanolamine salt of cetyl phosphate, sodium salt of lauryl phosphate, oleyl alcohol phosphate, cyclohexylamine salt of lauryl sulfate, cyclohexylamine salt of cetyl sulfate, oleic amide of N-methyl glucamine, polyoxyethylene sorbitan mono-oleate, polyoxyethylene sorbitan mono-laurate, polyoxyethylene oleic acid amide, guanidine oleate, phenyl guanidine stearate, di-(2-ethyl hexyl) guanidine sulfosuccinate and di-(Z-ethyl hexyl) triethanolamine sulfosuccinate.

Although white mineral oils having a paraffinic base and viscosity between 40 and 110 (as determined by a Saybolt Universal viscometer at a temperature of 100 F.) are preferred, naphthenic mineral oils can also be employed in. this invention.

A suitable emulsifier which will enable the finish of the present invention to be readily removed from fibrous materials can be selected by one of ordinary skill in the art from the many that are now commercially available. It is preferred, however, to use non-ionic surface-active compounds such as ethylene oxide adducts of straight chain aliphatic alcohols or acids which have from 12 to 18 carbon atoms. From 2 to 20 or more moles of ethylene oxide may be condensed with the aliphatic acid or alcohol and the resulting condensate may be esterified with a mole of a straight chain aliphatic acid having from 12 to 18 carbon atoms. These polyoxyethylene compounds are defined herein as dendro acids or alcohols with a number such as 6 or 12 preceding the dendro notation designating the number of moles of ethylene oxide which has been reacted with each mole acid or alcohol. Examples of suitable emulsifiers as defined by this terminology are 6 dendro lauric acid, 4 dendro lauric alcohol and 12 dendro oleic acid oleate. Other emulsifiers which are operative in this invention include sorbitan monooleate, hexaoxyethylene stearyl amine, deca-oxyethylene lauryl amine, triethanolamine oleate, diethanolamine palmitate, sulfated butyl oleate, octa-oxypropylene oleyl amine, hexa-oxyethylene sorbitan monooleate, hexa-oxyethylene sorbitan di-oleate, hexa-oxyethylene sorbitol mono-oleate, deca-oxyethylene nonyl phenol, cetyl alcohol sulfonate and dodecylbenzene sulfonate.

The finish composition of the presentinvention is applied to fibrous materials formed from hydrophobic cellulosic derivatives such as the lower-aliphatic acid esters of cellulose including cellulose formate, cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetate-butyrate and cellulose ethers including methyl,

ethyl and propyl cellulose. The term hydrophobic is utilized in a relative sense to indicate cellulosic derivatives such as those named above, which have a substantially lower afiinity for water than regenerated cellulose.

Only small amounts of the finish, i.e., from 0.1 to 5%. based on the weight of the fibrous material are necessary to impart the desirable properties to the fibrous material. The finish may be applied at any time to the formed materials but it is preferred to effect the appli-i Weight are illustrative of the present invention, the scope.

of the invention being limited only by the appended claims. In the following examples, the terminology: tallow-derived and coconut oil-derived N-hydrocarbon-trimethylene diamine dioleates refers to the aforesaid mixtures of dioleates wherein the hydrocarbon.

radicals of the former are derived from tallow fatty acids and the latter from coconut oil fatty acids in the manner: Thus the former consists essentially illustrated above. of a mixture of N-tetradecyl, N-hexadecyl, N-octadecyl, and N-octadecenyl trimethylene-diamine dioleates and the latter a mixture of N-octyl, N-decyl, N-dodecyl, N-tetradecyl, N-hexadecyl, N-octadecyl, and N-octadecenyl trimethylene-diamine dioleates.

Example 1 Five parts of cetyl ethyl morpholinium ethosulfate were dispersed in 10 parts of N-octadecyl-trirnethylenediamine dioleate and 5 parts of sorbitan mono-oleate (an emulsifier) were intimately mixed with the dispersion. The resulting mixture was uniformly dispersed in parts of white parafiinic mineral oil (viscosity 50 seconds) to form a composition suitable as a yarn finish.

Ten two-pound bobbins of cellulose acetate yarn of 75 denier and 20 filaments per yarn was treated with 2.8% by weight of the yarn to the above finish. The finish was applied to the individual filaments in the yarn by a coating roll in the spinning cell and the treated filaments collected and twisted /2 turn per inch. The treated yarn was well lubricated, soft and exhibited no tendency to pick up electrostatic charges. The finish was readily removed from the yarn by washing the same with a spray of water.

Example 2 Eight parts of oleyl imidazolinium ethosulfate was dispersed in 10 parts of N-hexadecyl-trimethylenediamine dioleate and to this dispersion was added 12 parts of an' emulsifier, 12 dendro oleic acid olea-te as in Example 1.

The mixture was uniformly dispersed in 70 parts of white parafiinic mineral oil (viscosity 60 seconds) and applied to cellulose acetate yarn as described in Example 1. The treated yarn was soft, well lubricated and easily knitted without picking up an electrostatic charge.

Example 3 Six parts of lauryl alcohol phosphate was dispersed in 10 parts of N-octadecenyl-trimethylenediamine dioleate and 9 parts of an emulsifier, 4 dendro lauryl alcohol were Example 4 Eight parts of the lauric amide of N-methyl glucamine' together with 12 parts of 6 dendro lauric acid were diskpersed in parts of Neoctadecyl-trimethylene 'diamine dioleate. The resulting dispersion was uniformly dispersed in 70 parts of white parafi'inic mineraloil-(viscosity 70 seconds). The above composition containing the anti-static agent, emulsifier, dioleate coupling agent and mineral oil was applied to cellulose acetate yarn substantially as described in Example 1.

Example 5 Five parts of cetyl ethyl morpholinium ethosulfate were dispersed in 10 parts of N-dodecyl-trimethylenediamine dioleate and 12 parts of 12 dendro oleic acid oleate were intimately mixed with the dispersion. The resulting mixture was uniformly dispersed in 80 parts of white mineral oil (viscosity 60 seconds) to form ayarnyfinish which was applied to cellulose acetate yarn in the man ner described in Example 1. The treated yarn was well lubricated, soft and exhibited no tendency to pick up electrostatic charges.

Example 6 Five parts of cetyl ethyl morpholinium acid chosphate were dispersed in 10 parts of a mixture of the above described tallow-derived N-hydrocarbon-trimethylene-diarnine dioleates and 10 parts of 4 dendro lorol alcohol (an emulsifier) were intimately mixed with the dispersion. The resulting mixture was uniformly dispersed in 75 parts of whiteparaflinic mineral oil (viscosity 50 seconds) and applied to cellulose acetate yarn as in Example 1. The treated yarn was well lubricated, soft and exhibited no tendency to pick up electrostatic charges. The finish was readily removed from the yarn by washing the same with a spray of water.

Example 7 Three parts of ethyl oleyl hydroxyethyl imidazolinium ethosulfate was dispersed in 5 parts of a mixture of tallow-derived N-hydrocarbon (described above) trimethylenediamine dioleates and to this dispersion was added 7 parts of an emulsifier, 3 dendro sorbitan dioleate as in Example 1. The mixture was uniformly dispersed in 85 parts of white parafiinic mineral oil (viscosity 50 seconds) and applied to cellulose acetate yarn as described in Example 1. The treated yarn was soft, well lubricated and easily knitted without picking up an electrostatic charge.

Example 8 Five parts of lauryl alcohol phosphate was dispersed in 10 parts of a mixture of coconut oil-derived N-hydrocarbon-trimethylenediamine dioleates. This mixture was then uniformly dispersed in 85 parts of white parafiinic mineral oil (viscosity 50 seconds) and applied to a yarn formed from cellulose acetate in the manner set forth in Example 1.

Example 9 Five parts of the lauric amide of N-methyl glucamine together with 10 parts of 6 dendro lauric acid were dispersed in 10 parts of a mixture of coconut oil-derived N-hydrocarbon-trimethylene diarnine dioleates. The resulting dispersion was uniformly dispersed in 75 parts of white parafiinic mineral oil (viscosity 50 seconds). The above composition containing the anti-static agent, emulsifier, dioleate coupling agent and mineral oil was applied to cellulose acetate yarn substantially as described in Example 1.

Example 10 Seven parts of lauryl alcohol phosphate were dispersed in 8 parts of a mixture of tallow-derived N-hydrocarbon-trimethylenediamine dioleates and 10 parts of 10 dendro oleic acid were intimately mixed with the dispersion. The resulting mixture was uniformly dispersed in 75 parts of white mineral oil (viscosity 50 seconds) to form a yarn finish which was applied to cellulose acetate yarn in the manner described in Excharges.

:ample "1. The treated yarn was well lubricated, soft and exhibited no tendency to pick up electrostatic Example 11 Five parts of the lauric amide of N-methyl glucamine were dispersed in 8 parts-of a mixture of tallow-derived N-hydrocarbon-trimethylenediamine dioleates. The resulting dispersion was uniformly dispersed'in 87 parts of white parafiinic mineral oil (viscosity 50 'seconds) *enediamine-as a coupling agent in yarn:finishes havin a mineral oil base. Unexpectedly, thedioleate also functioned as a softening agent withoutimpairing the strength of the yarn. The dioleate also minimized the corrosive effect of the finish where quaternary ammonium compounds were used as anti-static agents. {Another unexpected characteristic of fibrous materials ,treated in accordance with this invention is their non-abrasiveness when they are run over guide surfaces and the like. .'It was further noted that the dioleate improved the pickup of a gelatine size when applied to a treated yarn.

It is to be understood that the foregoing examples and description are illustrative 'and'that changes and variations may be made without departing from the spirit and scope of the invention as defined by the appended claims. The present application is a continuation-in-part of application Serial No. 455,770, now abandoned, filed September 13, 1954.

I claim:

1. A substantially anhydrous oil base finish composition for fibrous hydrophobic cellulose derivatives comprising mineral oil containing a normally oil-insoluble Water-soluble organic anti-static agent in a quantity sufficient to impart anti-static properties thereto and a coupling agent which makes said anti-static agent oil-dispersible having the general formula:

wherein R is selected from the group consisting of an aliphatic hydrocarbon radical containing 8 to 18 carbon atoms and mixtures of the same.

2. The combination of claim 1 wherein said coupling agent is N-octadecyl-trimethylenediamine dioleate.

3. The combination of claim 1 wherein said coupling agent is N-hexadecyl-trimethylenediamine dioleate.

4. The combination of claim 1 wherein said coupling agent is N-octadecenyl-trimethylenediamine dioleate.

5. The combination of claim 1 wherein said coupling agent is N-dodecyl-trimethylene dioleate.

6. The combination of claim 1 further characterized in that said coupling agent is a mixture of compounds having the formula of claim 1 and wherein R is a mixture of aliphatic hydrocarbon radicals having 14 to 18 carbon atoms.

7. The combination of claim 6 wherein R is a mixture of aliphatic hydrocarbon radicals consisting essentially of tetradecyl, hexadecyl, octadecyl, and octadecenyl radicals.

8. The combination of claim 1 further characterized in that said coupling agent is a mixture of compounds having the formula of claim 1 and wherein R is a mixture of aliphatic hydrocarbon radicals having 8 to 18 carbon atoms.

9. The combination of claim 8 wherein R is a mixture of aliphatic hydrocarbon radicals consisting essentially of octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, and octadecenyl radicals.

10. The combination of claim 1 wherein said composition comprises in parts by weight about 50 to about .ing;fibrous materialsformed from hydrophobic cellulose derivatives which comprises dispersing an oil-insoluble, ..water-soluble organic anti-static agent in the N-hydrocarbon-trimethylenediamine dioleate of claim 1 and mineral oil and applying the Composition of the mineral oil, anti-static agent and dioleate to fibrous materials formed from hydrophobic cellulose derivatives.

12. A process for lubricating, conditioning and softenling fibrous materials formed from hydrophobic cellulose derivatives which comprises dispersing from about 3 to 10 parts by weight of an oil-insoluble, water-soluble organic anti-static agent into from about 5 to about 17 .parts by weight of the coupling agent of claim 1, uniformly dispersing said mixture of said anti-static agent and said dioleate in from about 50 to about 90 parts by weight of mineral oil, and applying from about 0.1

to about 5% by weight of the resulting composition to fibrous materials formed from hydrophobic cellulose derivatives.

13. The process of claim 12 wherein said coupling agent is N:octadecyl-trimethylenediamine dioleate.

14. The process of claim 12 wherein said coupling agent is N-hexadecyl-trimethylenediamine dioleate.

15. The process of claim 12 wherein said coupling agent is N-octadecenyl-trimethylened-iamine dioleate.

16. The process of claim 12 wherein said coupling agent is N-dodecyl-trimethylenediamine dioleate.

17. The process of claim 12 wherein said coupling agent is a mixture of compounds and wherein R is a mixture of aliphatic hydrocarbon radicals having 13 to 18 carbon atoms.

18. The process of claim 17 wherein R is a mixture of aliphatic hydrocarbon radicals consisting essentially of tetradecyl, hexadecyl, octadecyl and octadecenyl radicals.

19. The process of claim 12 wherein said coupling agent is a mixture of compounds and wherein R is a mixture of aliphatic hydrocarbon radicals having 8 to 18 carbon atoms.

20. The process of claim 18 wherein R is a mixture of aliphatic hydrocarbon radicals consisting essentially of octyl,'decyl, dodecyl, tetradecyl, hexadecyl, octadecyl and octadecenyl radicals.

References Cited in the file of this patent UNITED STATES PATENTS 2,086,544 Dreyfus July 13, 1937 2,425,392 Robinson Aug. 12, 1947 2,695,270 Jefierson Nov. 23, 1954 FOREIGN PATENTS 328,675 Great Britain Apr. 30, 1930 

1. A SUBSTANTIALLY ANHYDROUS OIL BASE FINISH COMPOSITION FOR FIBROUS HYDROPHOBIC CELLULOSE DERIVATIVES COMPRISING MINERAL OIL CONTAINING A NORMALLY OIL-INSOLUBLE WATER-SOLUBLE ORGANIC ANTI-STATIC AGENT IN A QUANTITY SUFFICIENT TO IMPART ANTI-STATIC PROPERITES THERETO AND A COUPLING AGENT WHICH MAKES SAID ANTI-STATIC AGENT OIL-DISPERSIBLE HAVING THE GENERAL FORMULA: 